本发明公开了一种固态电池用聚合物电解质复合膜的制备方法，将金属有机框架材料、聚合物加入到有机溶剂中混合均匀，静电纺丝制成聚合物/MOF纤维复合膜；将PEO、Li(TFSI)溶解到乙腈中，通过溶液浇铸法制得PEO/Li(TFSI)复合薄膜；在聚四氟乙烯膜之间或表面以三明治结构分别放上PEO/Li(TFSI)复合薄膜、聚合物/MOF纤维复合膜、PEO/Li(TFSI)复合薄膜，热压后冷却得到固态电池用聚合物电解质复合膜。本发明利用PEO与Li(TFSI)的良好络合能力，聚合物/ MOFs纤维复合膜能提供支撑位点，以及MOFs的微孔结构能够提供有序的锂离子传导通道，可以将Li(TFSI)的阴离子固定在微孔通道中，加快阳离子传输，提高材料的电导率和耐高电压能力，使得材料电导率能够达到10‑4 S cm‑1，满足商业化全固态聚合物电解质对电导率的要求。
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